CN106008207A - Method for composite phosphotungstate catalyzed synthesis of citrate ester - Google Patents

Method for composite phosphotungstate catalyzed synthesis of citrate ester Download PDF

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Publication number
CN106008207A
CN106008207A CN201610376028.4A CN201610376028A CN106008207A CN 106008207 A CN106008207 A CN 106008207A CN 201610376028 A CN201610376028 A CN 201610376028A CN 106008207 A CN106008207 A CN 106008207A
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phosphotungstate
citrate
salt
catalyst
synthesizing
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CN106008207B (en
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周喜
袁浩坤
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Shaoyang University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to a method for composite phosphotungstate catalyzed synthesis of citrate ester. The citrate ester is synthesized through an esterification reaction of citric acid and fatty alcohol with composite phosphotungstate as a catalyst. The structure formula of the composite phosphotungstate adopted in the invention is (NH4)xM(3-x-y)/4HyPW12O40, wherein M is Ti or Zr, x is 0.4-1, and y is 0.4-1. The method has the following advantages: the catalyst has low cost, is easy to prepare, has a high catalysis efficiency, can be simply separated from the above product, and has excellent performances when being reused.

Description

A kind of method that compound phosphotungstate catalyzes and synthesizes citrate
Technical field
A kind of method that the present invention relates to synthesizing citric acid ester, catalyzes and synthesizes lemon particularly to a kind of compound phosphotungstate The method of lemon acid esters.
Background technology
Citrate is a kind of broad-spectrum nontoxic plasticizer, and it has nontoxic, and volatility is little, plasticizing efficiency height and phase The advantages such as capacitive is good.One of green succedaneum as traditional phthalic ester plasticizer, U.S. food and medicine prison Superintend and direct management board and have been approved by being applied to citric acid ester plasticizer packaging material for food, medical apparatus and personal hygiene article etc. Aspect.In recent years, citric acid ester type has become environment-friendlyplasticizer plasticizer first.
In the traditional processing technology of citrate, main employing concentrated sulphuric acid is catalyst.The low price of concentrated sulphuric acid, and Catalysis activity is higher.But, the by-product of reaction is more, causes bigger difficulty to the separating-purifying of product.Additionally, sulphuric acid pair Equipment corrosion is serious, and produces a large amount of acid-bearing wastewater, causes serious environmental pollution.In order to overcome disadvantages described above, grind both at home and abroad The person of studying carefully develops a series of solid acid catalyst for synthesizing citric acid ester, such as molecular sieve, solid super-strong acid, inorganic salt, sun Ion exchange resin and heteropoly acid etc..Wherein, heteropoly acid has green non-poisonous, activity and selectivity high, extensively applies In the reaction of synthesizing citric acid ester.But, heteropoly acid there is also that to be soluble in polar reaction medium, specific surface area low and thermally-stabilised The problem such as property is poor.Solution to the problems described above be by immobilized for heteropoly acid or be transformed into insoluble heteropoly acid salt catalysis Agent.Compared with carried heteropoly acid, heteropoly acid salt have acid strong, that surface acidity center density is high and easily prepared etc. is excellent Gesture, is the class heavy duty detergent solid acid catalyst that obtains extensive concern, as aluminium phosphotungstic acid (old equality, Industrial Catalysis, 2007, 15,46-49), 1-(3-sulfonic group) propyl group-3-Methylimidazole. phosphotungstate (Yu Shengjian etc., Industrial Catalysis, 2012,20, 52-55) etc. heteropolyacid salt catalyst has been applied in the reaction system of synthesizing citric acid ester the most.But, above-mentioned heteropoly acid salt Catalyst exists that activity is the highest, preparation process is complicated, large usage quantity or the defect such as repeat performance is poor.
CN 105061204 A uses molecular formula to be (NH4)xAgyH3-x-yPW12O40(x=0.3～0.8, y=0.3～0.8) Ammonium, silver-colored compound phosphotungstate catalyze and synthesize citrate, the activity of catalyst is higher than traditional unitary type ion doping phosphorus Wolframic acid, the yield of product is high, and catalyst is easily separated, and repeat performance is preferable.But, owing to the price of silver is higher so that it is Application is restricted.Therefore, exploitation is applicable to cheap, efficient, stable and easily prepared the consolidating of industrialized production citrate Body acid catalyst is the technical problem that those skilled in the art is in the urgent need to address.
Summary of the invention
It is an object of the invention to provide a kind of method that compound phosphotungstate catalyzes and synthesizes citrate, the method has There is production cost low, efficiently and the advantage such as environmental protection.
The method that the compound phosphotungstate that the present invention provides catalyzes and synthesizes citrate, with compound phosphotungstate for urging Agent, by citric acid and fatty alcohol generation esterification synthesizing citric acid ester, the skeleton symbol of described compound phosphotungstate is: (NH4)xM(3-x-y)/4HyPW12O40, wherein, M is Ti or Zr, x=0.4 ~ 1, y=0.4 ~ 1.
Further, described fatty alcohol is C4~C16Straight or branched fatty alcohol, more preferably n-butyl alcohol, hexanol, 2-Ethylhexyl Alcohol, n-octyl alcohol, Decanol or lauryl alcohol.
Further, the preparation process of described compound phosphotungstate catalyst includes step:
(1) ammonium salt, M salt being mixed in solution with phosphotungstic acid, wherein said M salt refers to titanium salt or zirconates；
(2) compound phosphotungstate described in isolated after reaction.
Further, described step (1) particularly as follows:
M salt is added in the aqueous solution of phosphotungstic acid；
Ammonium salt is added in aforementioned mixed solution.
Further, described ammonium salt is ammonium carbonate, ammonium hydrogen carbonate, ammonium chloride or ammonium nitrate.
Further, described M salt is titanium sulfate, zirconium nitrate or zirconium oxychloride.
Further, the temperature of described esterification is 120 ~ 170 DEG C.
Further, citric acid is 1:2 ~ 5 with the ratio of the amount of the material of fatty alcohol.
Further, catalyst is 0.5 ~ 3:100 with the mass ratio of citric acid.
Further, described (NH4)xM(3-x-y)/4HyPW12O40Replace with (NH4)xCu(3-x-y)/2HyPW12O40, and (NH4)xCu(3-x-y)/2HyPW12O40X=0.4 ~ 1, y=0.4 ~ 1.
Technical scheme provided by the present invention has the advantage that in (1) catalytic component without noble metal, low cost Honest and clean, it is easy to preparation, and catalytic efficiency is high；(2) catalyst separates with product simply, and catalyst can realize reusing；(3) lemon The yield of lemon acid esters is high.
Detailed description of the invention
Below the detailed description of the invention of the present invention is described in further detail.For those of skill in the art For Yuan, from detailed description of the invention, the above and other objects, features and advantages of the present invention will be apparent to.
Embodiment 1:
The preparation of catalyst: weigh 0.35 mmol ammonium carbonate, 0.4 mmol titanium sulfate and 1 mmol phosphotungstic acid and be dissolved in respectively In 20 ml deionized waters；After dissolving, room temperature and continuously stirred under conditions of, titanium sulfate solution is slowly added dropwise to phosphotungstic acid In solution, react 0.5 hour, then be slowly added dropwise sal volatile, increasingly generate white precipitate；After dripping, it is further continued for stirring React 0.5 hour, still aging 1 hour, after precipitation is separated by filtration, be dried, i.e. can get molecular formula for (NH4)0.7Ti0.4H0.7PW12O40Compound phosphotungstate.
Embodiment 2:
The preparation of catalyst: preparation process, with embodiment 1, only changes the addition of ammonium carbonate into 0.5 mmol, available molecule Formula is (NH4)1Ti0.4H0.4PW12O40Compound phosphotungstate.
Embodiment 3:
The preparation of catalyst: preparation process, with embodiment 1, only changes the addition of ammonium carbonate into 0.2 mmol, available molecule Formula is (NH4)0.4Ti0.4H1PW12O40Compound phosphotungstate.
Embodiment 4:
The preparation of catalyst: ammonium salt, with embodiment 1, is only changed into 0.5 mmol ammonium chloride, the addition of titanium sulfate by preparation process Changing 0.5 mmol into, available molecular formula is (NH4)0.5Ti0.5H0.5PW12O40Compound phosphotungstate.
Embodiment 5:
The preparation of catalyst: ammonium salt, with embodiment 4, is only changed into 0.5 mmol ammonium hydrogen carbonate by preparation process, and slaine changes 0.5 into Mmol zirconium nitrate, available molecular formula is (NH4)0.5Zr0.5H0.5PW12O40Compound phosphotungstate.
Embodiment 6:
The preparation of catalyst: ammonium salt, with embodiment 4, is only changed into 0.5 mmol ammonium nitrate by preparation process, and slaine changes 1 into Mmol copper nitrate, available molecular formula is (NH4)0.5Cu1H0.5PW12O40Compound phosphotungstate.
Embodiment 7:
19.21 g citric acids (0.1 mol), 29.6 g are added in the reactor being equipped with thermometer, water knockout drum and condensing tube (the NH of preparation in n-butyl alcohol (0.4 mol) and 0.29 g embodiment 14)0.7Ti0.4H0.7PW12O40Catalyst, opens stirring, rises Temperature, to 150 DEG C, starts timing, reacts 3 h when starting to occur backflow phenomenon in condensing tube.After reaction system is cooled to room temperature, Filtering and separate, filtrate uses gas chromatographic detection, and product yield is shown in Table 1.
Embodiment 8:
Use reaction condition same as in Example 7 and detection method, only the kind of catalyst is changed into preparation in embodiment 2 (NH4)1Ti0.4H0.4PW12O40Catalyst, product yield is shown in Table 1.
Embodiment 9:
Use reaction condition same as in Example 7 and detection method, only the kind of catalyst is changed into preparation in embodiment 3 (NH4)0.4Ti0.4H1PW12O40Catalyst, product yield is shown in Table 1.
Embodiment 10:
Use reaction condition same as in Example 7 and detection method, only the kind of catalyst is changed into preparation in embodiment 4 (NH4)0.5Ti0.5H0.5PW12O40Catalyst, product yield is shown in Table 1.
Embodiment 11:
Use reaction condition same as in Example 7 and detection method, only the kind of catalyst is changed into preparation in embodiment 5 (NH4)0.5Zr0.5H0.5PW12O40Catalyst, product yield is shown in Table 1.
Embodiment 12:
Use reaction condition same as in Example 7 and detection method, only the kind of catalyst is changed into preparation in embodiment 6 (NH4)0.5Cu1H0.5PW12O40Catalyst, product yield is shown in Table 1.
Embodiment 13:
19.21 g citric acids (0.1 mol), 26.05 g are added in the reactor being equipped with thermometer, water knockout drum and condensing tube (the NH of preparation in n-octyl alcohol (0.2 mol), 5 mL water entrainer hexamethylene and 0.29 g embodiment 14)0.7Ti0.4H0.7PW12O40Urge Agent, opens stirring, is warming up to 160 DEG C, starts timing when starting to occur backflow phenomenon in condensing tube, react 3 h.Reactant After system is cooled to room temperature, filtering and separate, filtrate uses liquid chromatographic detection, and product yield is shown in Table 1.
Embodiment 14:
Use the reaction condition identical with embodiment 13 and detection method, only raw material n-octyl alcohol is changed into 26.05 g 2-ethyl hexyls Alcohol (0.2 mol), product yield is shown in Table 1.
Embodiment 15:
Use the reaction condition identical with embodiment 13 and detection method, only raw material n-octyl alcohol is changed into 31.66 g Decanols (0.2 mol), product yield is shown in Table 1.
Embodiment 16:
Use the reaction condition identical with embodiment 13 and detection method, only raw material n-octyl alcohol is changed into 37.26 g lauryl alcohols (0.2 mol), is warming up to 165 DEG C, reacts 4 h, and product yield is shown in Table 1.
Embodiment 17:
Use reaction condition same as in Example 10 and detection method, only change the consumption of n-butyl alcohol into 14.8 g(0.2 Mol), product yield is shown in Table 1.
Embodiment 18:
Use reaction condition same as in Example 10 and detection method, only change the consumption of n-butyl alcohol into 22.2 g(0.3 Mol), product yield is shown in Table 1.
Embodiment 19:
Use reaction condition same as in Example 10 and detection method, only the consumption of n-butyl alcohol changed into 37 g(0.5 mol), Product yield is shown in Table 1.
Embodiment 20:
Use the reaction condition identical with embodiment 11 and detection method, only change the consumption of catalyst into 0.1 g, product yield It is shown in Table 1.
Embodiment 21:
Using the reaction condition identical with embodiment 11 and detection method, the consumption of catalyst only changes into 0.38 g, product is received Rate is shown in Table 1.
Embodiment 22:
Using reaction condition same as in Example 7 and detection method, only reaction temperature changes 130 DEG C into, product yield is shown in Table 1。
Embodiment 23:
Using reaction condition same as in Example 7 and detection method, only will change in the response time 5 hours, product yield is shown in Table 1。
Embodiment 24:
Catalyst after using in embodiment 7, filters after separating without any process, anti-for the circulation of next batch Should, the reaction condition of circular response is same as in Example 7 with detection method, and after recycling 15 times, product yield is shown in Table 1.
Comparative example 1:
Use reaction condition same as in Example 10 and detection method, only change catalyst into (NH4)2.5H0.5PW12O40, produce Thing yield is shown in Table 1.
Comparative example 2:
Use reaction condition same as in Example 10 and detection method, only change catalyst into Ti0.625H0.5PW12O40, product Yield is shown in Table 1.
Comparative example 3:
Use reaction condition same as in Example 10 and detection method, only change catalyst into Zr0.625H0.5PW12O40, product Yield is shown in Table 1.
Table 1: embodiment and the product yield of comparative example.
According to the result of table 1, the reaction of lactate synthesis citrate is had by the compound phosphotungstate that the present invention relates to The most excellent catalytic performance, its catalysis activity is better than traditional unitary type ion doping phosphotungstate, and catalyst is through 15 weights After multiple use, the phenomenon that activity is decreased obviously does not occurs.Additionally, catalyst is with low cost and easily prepared.Therefore, the present invention The technical scheme related to is suitable for industrial applications.It will be apparent to those skilled in the art that ammonium salt uses ammonium carbonate, bicarbonate Ammonium, ammonium chloride or ammonium nitrate, titanium salt, zirconates or mantoquita use nitrate, sulfate or chlorate, all can realize the skill of the present invention Art effect.The fatty alcohol that the present invention is suitable for includes the straight or branched fatty alcohol of C4 ~ C16.
Although should be appreciated that the present invention has carried out understanding explanation by above example, but without departing substantially from the present invention Spirit and essence in the case of, person of ordinary skill in the field when can according to the present invention make various corresponding change and Revise, but these corresponding variations and modifications all should belong to the scope of the claims of the present invention.

Claims (10)

1. the method that compound phosphotungstate catalyzes and synthesizes citrate, with compound phosphotungstate as catalyst, by lemon Lemon acid and fatty alcohol generation esterification synthesizing citric acid ester, it is characterised in that the skeleton symbol of described compound phosphotungstate For: (NH4)xM(3-x-y)/4HyPW12O40, wherein, M is Ti or Zr, x=0.4 ~ 1, y=0.4 ~ 1.
The method catalyzing and synthesizing citrate the most according to claim 1, it is characterised in that described fatty alcohol is positive fourth Alcohol, hexanol, 2-Ethylhexyl Alcohol, n-octyl alcohol, Decanol or lauryl alcohol.
The method catalyzing and synthesizing citrate the most according to claim 1, it is characterised in that described compound phosphotungstate The preparation process of catalyst includes step:
(1) ammonium salt, M salt being mixed in solution with phosphotungstic acid, wherein said M salt refers to titanium salt or zirconates；
(2) compound phosphotungstate described in isolated after reaction.
The method catalyzing and synthesizing citrate the most according to claim 3, it is characterised in that described step (1) particularly as follows:
M salt is added in the aqueous solution of phosphotungstic acid；
Ammonium salt is added in aforementioned mixed solution.
The method catalyzing and synthesizing citrate the most according to claim 3, it is characterised in that described ammonium salt be ammonium carbonate, Ammonium hydrogen carbonate, ammonium chloride or ammonium nitrate.
The method catalyzing and synthesizing citrate the most according to claim 3, it is characterised in that described M salt is titanium sulfate, nitre Acid zirconium or zirconium oxychloride.
7. according to the method catalyzing and synthesizing citrate described in any one of claim 1-6, it is characterised in that described esterification is anti- The temperature answered is 120 ~ 170 DEG C.
8. according to the method catalyzing and synthesizing citrate described in any one of claim 1-6, it is characterised in that citric acid and fat The ratio of the amount of the material of fat alcohol is 1:2 ~ 5.
9. according to the method catalyzing and synthesizing citrate described in any one of claim 1-6, it is characterised in that catalyst and lemon The mass ratio of lemon acid is 0.5 ~ 3:100.
The method catalyzing and synthesizing citrate the most according to claim 1, it is characterised in that described (NH4)xM(3-x-y)/ 4HyPW12O40Replace with (NH4)xCu(3-x-y)/2HyPW12O40, and (NH4)xCu(3-x-y)/2HyPW12O40X=0.4 ~ 1, y=0.4 ~ 1.
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Cited By (6)

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CN107188804A (en) * 2017-07-09 2017-09-22 邵阳学院 A kind of method that compound phosphotungstate catalyzes and synthesizes methyl oleate
CN108191814A (en) * 2018-01-27 2018-06-22 邵阳学院 A kind of method that phosphotungstic acid titanium ammonium compound salt catalyzes and synthesizes cyclohexanone ethylene ketal
CN110590589A (en) * 2019-10-25 2019-12-20 邵阳天堂助剂化工有限公司 Method for catalytic synthesis of ethylene bis stearamide by phosphotungstate
CN110655475A (en) * 2019-10-25 2020-01-07 邵阳天堂助剂化工有限公司 Method for synthesizing ethylene bis-stearamide by catalysis of composite doped heteropolyacid salt
CN110668966A (en) * 2019-10-25 2020-01-10 邵阳天堂助剂化工有限公司 Method for catalytic synthesis of ethylene bis stearamide by using quaternary ammonium titanium phosphotungstate
WO2020186421A1 (en) * 2019-03-18 2020-09-24 江南大学 Coordinate zirconium phosphotungstate catalyst and use thereof in catalytic hydrogenation of furfural

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Cited By (9)

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Publication number Priority date Publication date Assignee Title
CN107188804A (en) * 2017-07-09 2017-09-22 邵阳学院 A kind of method that compound phosphotungstate catalyzes and synthesizes methyl oleate
CN107188804B (en) * 2017-07-09 2021-01-26 邵阳学院 Method for catalytically synthesizing methyl oleate by using composite phosphotungstate
CN108191814A (en) * 2018-01-27 2018-06-22 邵阳学院 A kind of method that phosphotungstic acid titanium ammonium compound salt catalyzes and synthesizes cyclohexanone ethylene ketal
CN108191814B (en) * 2018-01-27 2021-03-30 邵阳学院 Method for synthesizing cyclohexanone ethylene ketal under catalysis of titanium ammonium phosphotungstate composite salt
WO2020186421A1 (en) * 2019-03-18 2020-09-24 江南大学 Coordinate zirconium phosphotungstate catalyst and use thereof in catalytic hydrogenation of furfural
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CN110590589A (en) * 2019-10-25 2019-12-20 邵阳天堂助剂化工有限公司 Method for catalytic synthesis of ethylene bis stearamide by phosphotungstate
CN110655475A (en) * 2019-10-25 2020-01-07 邵阳天堂助剂化工有限公司 Method for synthesizing ethylene bis-stearamide by catalysis of composite doped heteropolyacid salt
CN110668966A (en) * 2019-10-25 2020-01-10 邵阳天堂助剂化工有限公司 Method for catalytic synthesis of ethylene bis stearamide by using quaternary ammonium titanium phosphotungstate

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